EP0310704A2 - Reactive thixotropic hot-melt adhesive based on silane - Google Patents

Reactive thixotropic hot-melt adhesive based on silane Download PDF

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Publication number
EP0310704A2
EP0310704A2 EP87116213A EP87116213A EP0310704A2 EP 0310704 A2 EP0310704 A2 EP 0310704A2 EP 87116213 A EP87116213 A EP 87116213A EP 87116213 A EP87116213 A EP 87116213A EP 0310704 A2 EP0310704 A2 EP 0310704A2
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EP
European Patent Office
Prior art keywords
melt adhesive
hot melt
diisocyanate
glycol
silane
Prior art date
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Granted
Application number
EP87116213A
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German (de)
French (fr)
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EP0310704A3 (en
EP0310704B1 (en
Inventor
Peter W. Dr. Merz
Lutz-Dieter Zabel
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Sika Schweiz AG
Sika AG
Original Assignee
Sika AG
Sika AG Vorm Kaspar Winkler and Co
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0016—Plasticisers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2170/00—Compositions for adhesives
    • C08G2170/20—Compositions for hot melt adhesives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/28—Non-macromolecular organic substances

Definitions

  • the present invention relates to a reactive, thixotropic, hot melt adhesive based on silane.
  • Hot melts are traditionally thermoplastic materials that are heated to 90-200 ° C for processing in a pistol or other device and applied as a liquid mass to the substrates to be bonded.
  • thermoplastic behavior has proven to be a disadvantage, since their mechanical and thus adhesive properties are strongly temperature-dependent. At higher temperatures they soften again and tend to become brittle at low temperatures, which is why they are only used in a rather narrow temperature range.
  • Reactive polyurethane hot melt adhesives have been introduced on the market in recent years. These are characterized by the fact that they lose their thermoplasticity after crosslinking and provide good mechanical properties in a wide temperature range.
  • the reactive isocyanate groups can be crosslinked by means of water, in particular atmospheric moisture, or by means of an H-active compound released by heat.
  • the known solvent-free, moisture-curing prepolymeric isocyanates are liquid to soft-wax-like at room temperature and, due to their low initial strength and long reaction time, have only limited application possibilities.
  • the reactive hot melt adhesive described there preferably tough and plastically deformable at room temperature, contains a mixture of: at least one thermoplastic material, preferably in an amount of 20 to 90% by weight, in particular 50 to 65% by weight, - At least one isocyanate-based binder, preferably in an amount of 5 to 40% by weight, in particular 15 to 30% by weight, and at least one thixotropic agent, preferably in an amount of 3 to 30% by weight, in particular 8 to 20% by weight, and the isocyanate content, based on the total hot melt adhesive, is in the range from 0.01 to 10% by weight, preferably in the range from 0.1 to 1% by weight, in particular in the range from 0.3 to 0.7% .-%.
  • At least one plasticizer, at least one filler and at least one additive, such as adhesion promoters, catalysts, etc., can be mixed into these hotmelt adhesives.
  • the object of the present invention is to further improve the status achieved in Swiss patent application No. 1902 / 86-4 and to develop reactive hotmelt adhesives which have no properties which are hazardous to health. This could be achieved by completely dispensing with materials containing isocyanate groups and replacing them with the less harmful silane groups.
  • the thixotropic, silane group-reactive, deformable hot-melt adhesive that is still tough-plastic after cooling is characterized in that that he's a mix of - at least one thermoplastic material, and contains at least one thixotropic agent, wherein silane groups are contained either in the thermoplastic material itself or in at least one additionally incorporated binder based on silane.
  • the thixotropic, silane group-reactive hot melt adhesive according to the invention can be used to bond and / or seal one or more materials of the same or different properties to form a composite.
  • this reactive hot melt adhesive can also be used with the help of an extruder to a profile of any shape, such as a cord, a tape, etc., are deformed at elevated temperature.
  • these preformed cords can be done by hand by hand and is far more cost-effective, quality-assured, faster and cleaner compared to the effort with pasty materials.
  • These reactive cords can be rolled up in a snail shape and packed in an aluminum bag as a water vapor barrier so that they can also be used in the do-it-yourself market.
  • a silane binder which is composed of the components of polyoxypropylene ether diol with a molecular weight of 2000 and 4,4′-diphenylmethane diisocyanate, are successively combined with an NCO to the thermoplastic described above. Content 1.0%, blocked with 55 parts of Dynasilan 1110, N-methyl-3-aminopropyltrimethoxysilane, and 490 parts of carbon black dried at 130 ° C. and 4.8 parts of Niax D 22 (dibutyltin dilaurate).
  • This non-threadlike mass produced in this way is slightly sticky and stable at the production temperature and is easy to grip and plastically deformable at room temperature.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

A thixotropic hot-melt adhesive contains reactive silane groups and is still viscous and plastically moldable after cooling. It contains a mixture of at least one thermoplastic material, and at least one thixotropic agent, wherein silane groups are contained either in the thermoplastic material itself or in at least one added silane-based binder.

Description

Die vorliegende Erfindung bezieht sich auf einen reaktiven, thixotropierten Schmelzklebstoff auf Silan-­Basis.The present invention relates to a reactive, thixotropic, hot melt adhesive based on silane.

Traditionell sind Schmelzklebstoffe (Hot Melts) thermoplastische Materialien, die zur Verarbeitung in einer Pistole oder einer anderen Vorrichtung auf 90-200° C erhitzt und als flüssige Masse auf die zu verklebenden Substrate aufgetragen werden.Hot melts are traditionally thermoplastic materials that are heated to 90-200 ° C for processing in a pistol or other device and applied as a liquid mass to the substrates to be bonded.

Beim Erkalten erstarrt die Masse und bildet so rasch eine feste Verklebung.When it cools, the mass solidifies and quickly forms a firm bond.

Das schnelle Verfestigen und das Fehlen von Wasser und Lösungsmitteln bevorteilen diese Schmelzkleber gegenüber anderen Klebstoffsystemen.The rapid solidification and the lack of water and solvents give these hot melt adhesives an advantage over other adhesive systems.

Als ein Nachteil hat sich ihr thermoplastisches Verhalten erwiesen, da ihre mechanischen und somit haf­tenden Eigenschaften stark temperaturabhängig sind. Bei erhöhter Temperatur erweichen sie wieder und neigen bei tiefer Temperatur zur Versprödung, weshalb sie nur in einem eher engen Temperaturbereich eingesetzt werden.Their thermoplastic behavior has proven to be a disadvantage, since their mechanical and thus adhesive properties are strongly temperature-dependent. At higher temperatures they soften again and tend to become brittle at low temperatures, which is why they are only used in a rather narrow temperature range.

In den letzten Jahren sind reaktive Polyuretha­nen-Schmelzklebstoffe auf dem Markt eingeführt worden. Diese zeichnen sich dadurch aus, dass sie nach Vernetzung ihre Thermoplastizität verlieren und gute mechanische Eigenschaften in einem breiten Temperaturbereich liefern. Die Vernetzung der reaktiven Isocyanatgruppen kann mit­tels Wasser, insbesondere Luftfeuchtigkeit, oder durch eine durch Wärme freigesetzte H-aktive Verbindung erfol­gen.Reactive polyurethane hot melt adhesives have been introduced on the market in recent years. These are characterized by the fact that they lose their thermoplasticity after crosslinking and provide good mechanical properties in a wide temperature range. The reactive isocyanate groups can be crosslinked by means of water, in particular atmospheric moisture, or by means of an H-active compound released by heat.

Die bekannten lösungsmittelfreien, feuchtig­keitshärtenden präpolymeren Isocyanate sind bei Raumtem­peratur flüssig bis weich-wachsähnlich und haben aufgrund ihrer niedrigen Anfangsfestigkeit und der langen Reak­tionszeit nur begrenzte Einsatzmöglichkeiten.The known solvent-free, moisture-curing prepolymeric isocyanates are liquid to soft-wax-like at room temperature and, due to their low initial strength and long reaction time, have only limited application possibilities.

Aus der DE-PS 24 01 320 sind isocyanathaltige Schmelzkleber bekannt, welche zusammengesetzt sind aus:

  • a) 20 bis 73 Gew.-% eines Urethan-Präpolymeren mit terminalen Isocyanat-Gruppen der beiden Enden,
  • b) 2 bis 25 Gew.-% eines thermoplastischen Polymeren aus der Gruppe der Aethylen-Vinylacetat-Copoly­meren, der Aethylen-Acrylsäure-Copolymeren, der Aethylen-­Acrylat-Copolymeren, des ataktischen Polypropylens und der linearen Polyäthylenterephthalat-Polymeren sowie
  • c) 25 bis 55 Gew.-% eines klebrigmachenden Harzes wie Kolophoniumderivate oder Terpenphenol-Copoly­mere.
From DE-PS 24 01 320 hot melt adhesives containing isocyanate are known, which are composed of:
  • a) 20 to 73% by weight of a urethane prepolymer with terminal isocyanate groups at the two ends,
  • b) 2 to 25 wt .-% of a thermoplastic polymer from the group of ethylene-vinyl acetate copolymers, the ethylene-acrylic acid copolymers, the ethylene-acrylate copolymers, the atactic polypropylene and the linear polyethylene terephthalate polymers and
  • c) 25 to 55% by weight of a tackifying resin such as rosin derivatives or terpene phenol copolymers.

Gemische aus diesen Komponenten neigen aber bei bestimmten Mischungsverhältnissen zur Unverträglichkeit und zur Instabilität der Schmelzen und besitzen ungenü­gende Standfestigkeiten. Ebenfalls ist ihre Lagerstabili­tät oft nicht ausreichend.Mixtures of these components tend to be incompatible and to instability of the melts at certain mixing ratios and have inadequate stability. Their storage stability is also often not sufficient.

In der DE-OS 32 36 313 sind reaktive Schmelz­kleber beschrieben, welche verträgliche, schmelzstabile, unter Luftfeuchtigkeitsausschluss lagerstabile Mischungen darstellen und eine grosse Anfangshaftfestigkeit und eine hohe Thermostabilität aufweisen. Diese reaktiven Schmelz­kleber wurden entwickelt für die Verklebung von thermo­plastischen und duroplastischen Kunststoffen, Schaumstof­fen, lackierten Oberflächen, Holz, Papier, Leder, Gummi, Textilien, Metalle, usw. und bestehen aus einer Mischung aus:

  • a) 20 bis 90 Gew.-% eines präpolymeren Iso­cyanats,
  • b) 0 bis 75 Gew.-% eines thermoplastischen Polyurethans
    sowie
  • c) 5 bis 50 Gew.-% eines niedrigmolekularen Kunstharzes aus der Gruppe der Ketonharze und/oder Keton-­Aldehyd-Kondensationsharze und/oder Hydrierungsprodukte von Acetophenon-Kondensationsharzen.
DE-OS 32 36 313 describes reactive hotmelt adhesives which are compatible, melt-stable mixtures which are stable in storage under the exclusion of atmospheric moisture and have great initial adhesive strength and high thermal stability. These reactive hot melt adhesives were developed for the bonding of thermoplastic and thermosetting plastics, foams, painted surfaces, wood, paper, leather, rubber, textiles, metals, etc. and consist of a mixture of:
  • a) 20 to 90% by weight of a prepolymeric isocyanate,
  • b) 0 to 75% by weight of a thermoplastic polyurethane
    such as
  • c) 5 to 50 wt .-% of a low molecular weight synthetic resin from the group of ketone resins and / or ketone-aldehyde condensation resins and / or hydrogenation products of acetophenone condensation resins.

Diese reaktiven Schmelzkleber mit den oben angegebenen Mischungsmöglichkeiten sind beim Auftrag wenig standfest - d.h. eine Auftragsdicke von mehr als 2 mm kann nicht gewährleistet werden -, stark klebrig und fädig, und nach Abkühlung zäh und schlecht plastisch verformbar. Ihr Einsatz ist somit auf bestimmte Anwen­dungsgebiete begrenzt.These reactive hot melt adhesives with the above-mentioned mixing options are not very stable when applied - i.e. an application thickness of more than 2 mm can not be guaranteed -, very sticky and thready, and tough and difficult to plastically deform after cooling. Their use is therefore limited to certain areas of application.

Dieser unzulängliche Stand der Technik wird mit der Schweizerischen Patentanmeldung Nr. 1902/86-4 über­wunden, und reaktive Schmelzklebstoffe werden beschrieben, die beim Auftrag standfest, nach Abkühlung auf Raumtempe­ratur anfassbar und plastisch verformbar sind und nach der Vernetzung mit Wasser, insbesondere Luftfeuchtigkeit, gute mechanische, gummi- bis zähelastische und haftende Eigenschaften unabhängig von der Applikationstemperatur, d.h. der Schmelz- bzw. Raumtemperatur besitzen. Aufgrund seiner Standfestigkeit bei Applikation ist ein erweitertes Anwendungsgebiet zugänglich, insbesondere Klebungen im Autoindustriebereich z.B. Einkleben von Windschutzscheiben, Ankleben von Kunststoffleisten usw., und Klebungen im Schiffsbau, z.B. Verkleben von Holzteilen.This inadequate state of the art is overcome with the Swiss patent application No. 1902 / 86-4, and reactive hotmelt adhesives are described which are stable on application, can be handled and plastically deformed after cooling to room temperature, and are good after crosslinking with water, in particular atmospheric humidity mechanical, rubber to tough and elastic and adhesive properties regardless of the application temperature, ie have the melting or room temperature. Due to its stability during application, an extended area of application is accessible, in particular adhesives in the automotive industry e.g. Gluing in windshields, gluing plastic strips, etc., and gluing in shipbuilding, e.g. Gluing wooden parts.

In der Schweizerischen Patentanmeldung Nr. 1902/­86-4 wird ebenfalls ein Verfahren zur Herstellung dieses reaktiven Schmelzklebstoffes zur Verfügung gestellt. Der dort beschriebene reaktive - vorzugsweibe bei Raumtempe­ratur zäh-plastisch verformbare - Schmelzklebstoff ent­hält ein Gemisch aus:
- wenigstens einem thermoplastischen Material, vorzugsweise in einer Menge von 20 bis 90 Gew.-%, insbe­sondere 50 bis 65 Gew.-%,
- wenigstens einem Bindemittel auf Isocyanatba­sis, vorzugsweise in einer Menge von 5 bis 40 Gew.-%, insbesondere 15 bis 30 Gew.-%, und
- wenigstens einem Thixotropiermittel, vorzugs­weise in einer Menge von 3 bis 30 Gew.-%, insbesondere 8 bis 20 Gew.-%,
und der Isocyanatgehalt, bezogen auf den gesam­ten Schmelzklebstoff, liegt im Bereich von 0,01 bis 10 Gew.-%, vorzugsweise im Bereich von 0,1 bis 1 Gew.-%, insbesondere im Bereich von 0,3 bis 0,7 Gew.-%.Swiss patent application No. 1902 / 86-4 also provides a process for producing this reactive hot melt adhesive. The reactive hot melt adhesive described there, preferably tough and plastically deformable at room temperature, contains a mixture of:
at least one thermoplastic material, preferably in an amount of 20 to 90% by weight, in particular 50 to 65% by weight,
- At least one isocyanate-based binder, preferably in an amount of 5 to 40% by weight, in particular 15 to 30% by weight, and
at least one thixotropic agent, preferably in an amount of 3 to 30% by weight, in particular 8 to 20% by weight,
and the isocyanate content, based on the total hot melt adhesive, is in the range from 0.01 to 10% by weight, preferably in the range from 0.1 to 1% by weight, in particular in the range from 0.3 to 0.7% .-%.

Zusätzlich können in diesen Schmelzklebstoffen wenigstens ein Weichmacher, wenigstens ein Füllstoff und wenigstens ein Zusatzstoff, wie Haftvermittler, Kataly­satoren usw., eingemischt sein.In addition, at least one plasticizer, at least one filler and at least one additive, such as adhesion promoters, catalysts, etc., can be mixed into these hotmelt adhesives.

Aufgabe der vorliegenden Erfindung ist es, den in der Schweizerischen Patentanmeldung Nr. 1902/86-4 er­reichten Stand weiter zu verbessern und reaktive Schmelz­klebstoffe zu entwickeln, die keine gesundheitlich gefähr­denden Eigenschaften aufweisen. Dies konnte dadurch er­reicht werden, dass auf Isocyanatgruppen enthaltende Ma­terialien gänzlich verzichtet wurde und diese durch die weniger gesundheitlich gefährdenden Silangruppen ersetzt wurden.The object of the present invention is to further improve the status achieved in Swiss patent application No. 1902 / 86-4 and to develop reactive hotmelt adhesives which have no properties which are hazardous to health. This could be achieved by completely dispensing with materials containing isocyanate groups and replacing them with the less harmful silane groups.

Der erfindungsgemässe, thixotropierte, Silangrup­pen-reaktive, nach dem Abkühlen noch zäh-plastische, ver­formbare Schmelzklebstoff ist dadurch gekennzeichnet,
dass er ein Gemisch aus
- wenigstens einem thermoplastischen Material,
und
- wenigstens einem Thixotropiermittel enthält,
wobei Silangruppen entweder im thermoplastischen Material selbst oder in wenigstens einem, noch zusätzlich einge­brachten Bindemittel auf Silanbasis enthalten sind.The thixotropic, silane group-reactive, deformable hot-melt adhesive that is still tough-plastic after cooling is characterized in that
that he's a mix of
- at least one thermoplastic material,
and
contains at least one thixotropic agent,
wherein silane groups are contained either in the thermoplastic material itself or in at least one additionally incorporated binder based on silane.

Bevorzugte Ausführungsformen des erfindungsge­ mässen Schmelzklebstoffes sind in den abhängigen Ansprü­chen definiert.Preferred embodiments of the fiction hot melt adhesive are defined in the dependent claims.

Das erfindungsgemässe Verfahren zur Herstellung des erfindungsgemässen thixotropierten, Silangruppen­reaktiven Schmelzklebstoffes ist dadurch gekennzeichnet, dass man unter wasserfreien Bedingungen entweder

  • a) ein thermoplastisches, Silangruppen enthal­tendes Material vorlegt oder es in situ vor oder nach der Hinzugabe von weiteren Komponenten erzeugt, und danach beim Erwei­chungspunkt das Thixotropiermittel homogen einmischt, oder
  • b) wenigstens ein Isocyanatgruppen und Silan­gruppen enthaltendes Material mit wenigstens einem Thixo­tropiermittel vermischt, danach wenigstens eine minde­stens di-H-aktive Verbindung hinzugibt und die Isocyanat­gruppen in situ umsetzt, oder
  • c) ein thermoplastisches, keine Silangruppen ent­haltendes Material vorlegt oder es in situ erzeugt, da­nach beim Erweichungspunkt das keine Isocyanatgruppen ent­haltende Bindemittel auf Silanbasis und das Thixotropier­mittel homogen einmischt, und
    die gemäss obigen Varianten a) bis c) hergestell­ten Gemische auf Umgebungstemperatur erkalten lässt.
The process according to the invention for producing the thixotropic, silane group-reactive hot melt adhesive according to the invention is characterized in that either under anhydrous conditions
  • a) presenting a thermoplastic material containing silane groups or producing it in situ before or after the addition of further components, and then homogeneously mixing in the thixotropic agent at the softening point, or
  • b) at least one material containing isocyanate groups and silane groups is mixed with at least one thixotropic agent, then at least one at least di-H-active compound is added and the isocyanate groups are reacted in situ, or
  • c) presenting a thermoplastic material containing no silane groups or producing it in situ, then homogeneously mixing in the silane-based binder containing no isocyanate groups and the thixotropic agent at the softening point, and
    the mixtures prepared according to variants a) to c) above can cool to ambient temperature.

Bevorzugte Ausführungsformen des erfindungsge­mässen Verfahrens sind in den abhängingen Verfahrensan­sprüchen definiert.Preferred embodiments of the method according to the invention are defined in the dependent method claims.

Der erfindungsgemässe, thixotropierte, Silangrup­pen-reaktive Schmelzklebstoff kann zum Verkleben und/oder Abdichten von einen oder mehreren Materialien gleicher oder ungleicher Beschaffenheit zu einem Verbund verwendet werden.The thixotropic, silane group-reactive hot melt adhesive according to the invention can be used to bond and / or seal one or more materials of the same or different properties to form a composite.

Bevorzugte Verwendungen der erfindungsgemässen Schmelzklebstoffe sind in den abhängigen Verwendungsan­sprüchen definiert.Preferred uses of the hotmelt adhesives according to the invention are defined in the dependent use claims.

Neben dem direkten Auftrag bei der Erweichungs­temperatur kann z.B. auch dieser reaktive Schmelzkleb­ stoff mit Hilfe eines Extruders zu einem Profil beliebi­ger Form, wie z.B. eine Schnur, ein Band, usw., bei erhöhter Temperatur verformt werden.In addition to direct application at the softening temperature, this reactive hot melt adhesive can also be used with the help of an extruder to a profile of any shape, such as a cord, a tape, etc., are deformed at elevated temperature.

Zur Verklebung kann die Applikation dieser vorgeformten Schnüre ohne maschinellen Aufwand durch Auflegen von Hand erfolgen und ist im Vergleich zum Auf­wand bei pastösen Materialien weit kostengünstiger, qualitätssicherer, schneller und sauberer.For gluing, the application of these preformed cords can be done by hand by hand and is far more cost-effective, quality-assured, faster and cleaner compared to the effort with pasty materials.

Diese reaktiven Schnüre können schneckenförmig aufgerollt und in einem Aluminiumbeutel als Wasserdampf­barriere lagerungsfähig verpackt werden und finden somit auch Eingang im Do-it-yourself-Markt.These reactive cords can be rolled up in a snail shape and packed in an aluminum bag as a water vapor barrier so that they can also be used in the do-it-yourself market.

Die nachfolgenden Ausführungsbeispiele dienen der Illustration der Erfindung. Die Angabe der Teile beziehen sich auf das Gewicht.The following exemplary embodiments serve to illustrate the invention. The details of the parts refer to the weight.

Ausführungsbeispiel 1Embodiment 1 1. Beschreibung der Herstellung des Polyure­thanthermoplastes1. Description of the manufacture of the polyurethane thermoplastic

In einer Mischung aus 2400 Teilen eines Poly­oxypropylenetherdiols vom Molekulargewicht 2000 und 580 Teilen Diisodecylphthalat werden bei Raumtemperatur 641,8 Teile 4,4′-Diphenylmethan-diisocyanat suspendiert und die Suspension unter Rühren und Luftfeuchtigkeitsausschluss auf 80°C erwärmt, wobei das kristalline 4,4′-Diphenylme­thandiisocyanat in Lösung geht.In a mixture of 2400 parts of a polyoxypropylene ether diol with a molecular weight of 2000 and 580 parts of diisodecyl phthalate, 641.8 parts of 4,4'-diphenylmethane diisocyanate are suspended at room temperature and the suspension is heated to 80 ° C. with stirring and exclusion of air humidity, the crystalline 4,4 '-Diphenylmethane diisocyanate goes into solution.

Nach ca. 150 Minuten werden 114,1 Teile 1,4-Bu­tandiol zugegeben und die Reaktionsmischung nach Tempe­raturerhöhung auf ca. 100°C bis zur Konsistenz des Iso­cyanatgehaltes, ca. 1 Stunde, gerührt.After approx. 150 minutes, 114.1 parts of 1,4-butanediol are added and the reaction mixture is stirred after the temperature has been raised to approx. 100 ° C. until the isocyanate content is approx. 1 hour.

2. Beschreibung der Herstellung des reaktiven Schmelzklebstoffes2. Description of the manufacture of the reactive hot melt adhesive

Bei einer Temperatur von 100°C werden zum oben beschriebenen Thermoplast nacheinander 1100 Teile eines Silan-Bindemittels, das aus den Komponenten Polyoxy­propylenetherdiol vom Molekulargewicht von 2000 und 4,4′-­Diphenylmethandiisocyanat aufgebaut ist, mit einem NCO-­ Gehalt 1,0 %, abgeblockt mit 55 Teilen Dynasilan 1110, N-Methyl-3-aminopropyltrimethoxysilan, und 490 Teile bei 130°C getrockneter Russ und 4,8 Teile Niax D 22 (Dibutyl­zinndilaurat) eingemischt. Diese so hergestellte, nicht fädige Masse ist bei der Herstellungstemperatur leicht klebrig und standfest und bei Raumtemperatur gut anfass­bar und plastisch verformbar.At a temperature of 100 ° C., 1100 parts of a silane binder, which is composed of the components of polyoxypropylene ether diol with a molecular weight of 2000 and 4,4′-diphenylmethane diisocyanate, are successively combined with an NCO to the thermoplastic described above. Content 1.0%, blocked with 55 parts of Dynasilan 1110, N-methyl-3-aminopropyltrimethoxysilane, and 490 parts of carbon black dried at 130 ° C. and 4.8 parts of Niax D 22 (dibutyltin dilaurate). This non-threadlike mass produced in this way is slightly sticky and stable at the production temperature and is easy to grip and plastically deformable at room temperature.

Folgende analytische Daten wurden nach 2-wöchi­ger Lagerung der Masse bei 23°C und 50% relativer Luft­feuchtigkeit ermittelt: Härte Shore A 30 (DIN 53505) Zugfestigkeit [N/mm²] 2,2 (DIN 53504) Bruchdehnung [%] 350 (DIN 53504) Bruchspannung [N/mm²] 2,2 (DIN 53504) Weiterreissfestigkeit [N/mm²] 6,2 (DIN 53515) offene Liegezeit der Raupen ca. 1/2 Std. Gebrauchstemperatur -40°C bis +90°C (temporär bis +150°C) The following analytical data were determined after the mass had been stored for 2 weeks at 23 ° C. and 50% relative atmospheric humidity: Shore A hardness 30th (DIN 53505) Tensile strength [N / mm²] 2.2 (DIN 53504) Elongation at break [%] 350 (DIN 53504) Breaking stress [N / mm²] 2.2 (DIN 53504) Tear resistance [N / mm²] 6.2 (DIN 53515) open crawler lay time about 1/2 hour Operating temperature -40 ° C to + 90 ° C (temporarily up to + 150 ° C)

Ausführungsbeispiel 2Embodiment 2

In einer Mischung aus 2400 Teilen eines Poly­oxypropylenetherdiols vom Molekulargewicht 2000 und 580 Teilen Diisodecylphthalat werden bei Raumtemperatur 641,8 Teile 4,4′-Diphenylmethan-diisocyanat suspendiert und die Suspension unter Rühren und Luftfeuchtigkeitsausschluss auf 80°C erwärmt, wobei das kristalline, 4,4′-Diphenylme­thandiisocyanat in Lösung geht.In a mixture of 2400 parts of a polyoxypropylene ether diol with a molecular weight of 2000 and 580 parts of diisodecyl phthalate, 641.8 parts of 4,4'-diphenylmethane diisocyanate are suspended at room temperature and the suspension is heated to 80 ° C. with stirring and exclusion of humidity, the crystalline, 4, 4'-diphenylmethane diisocyanate goes into solution.

Nach ca. 150 Minuten werden 97,3 Teile 1,4-Bu­tandiol zugegeben und die Reaktionsmischung nach Tempe­raturerhöhung auf ca. 100°C bis zur Konsistenz des Iso­cyanatgehaltes, ca. 1 Stunde, gerührt.After approx. 150 minutes, 97.3 parts of 1,4-butanediol are added and the reaction mixture, after increasing the temperature to approx. 100 ° C., is stirred until the isocyanate content is approx. 1 hour.

Bei einer Temperatur von 100°C werden nacheinan­der 53,5 Teile Dynasilan 1110, N-Methyl-3-aminopropyltri­ methoxysilan, und 250 Teile bei 130°C getrockneter Russ und 2,5 Teile Niax D 22 (Dibutylzinndilaurat) eingemischt. Diese so hergestellte, nicht fädige Masse ist bei der Her­stellungstemperatur leicht klebrig und standfest und bei Raumtemperatur gut anfassbar und plastisch verformbar.At a temperature of 100 ° C 53.5 parts of Dynasilan 1110, N-methyl-3-aminopropyltri methoxysilane, and 250 parts of carbon black dried at 130 ° C and 2.5 parts of Niax D 22 (dibutyltin dilaurate) mixed. This non-threadlike mass produced in this way is slightly sticky and stable at the production temperature and is easy to grip and plastically deformable at room temperature.

Folgende analytische Daten wurden nach 2-wöchi­ger Lagerung der Ma-se bei 23°C und 50 % relativer Luft­feuchtigkeit ermittelt: Härte Shore A 45 (DIN 53505) Zugfestigkeit [N/mm²] 5,8 (DIN 53504) Bruchdehnung [%] 580 (DIN 53504) Bruchspannung [N/mm²] 5,8 (DIN 53504) Weiterreissfestigkeit [N/mm²] 9,4 (DIN 53515) offene Liegezeit der Raupen ca. 1/2 Std. Gebrauchstemperatur -40°C bis +90°C (temporär bis +150°C) The following analytical data were determined after the mass had been stored for 2 weeks at 23 ° C. and 50% relative atmospheric humidity: Shore A hardness 45 (DIN 53505) Tensile strength [N / mm²] 5.8 (DIN 53504) Elongation at break [%] 580 (DIN 53504) Breaking stress [N / mm²] 5.8 (DIN 53504) Tear resistance [N / mm²] 9.4 (DIN 53515) open crawler lay time about 1/2 hour Operating temperature -40 ° C to + 90 ° C (temporarily up to + 150 ° C)

Claims (16)

1. Thixotropierter, Silangruppen-reaktiver, nach dem Abkühlen noch zäh-plastischer verformbarer Schmelzklebstoff, dadurch gekennzeichnet, dass er ein Ge­misch aus
- wenigstens einem thermoplastischen Material,
und
- wenigstens einem Thixotropiermittel enthält,
wobei Silangruppen entweder im thermoplastischen Material selbst oder in wenigstens einem noch zusätzlich einge­brachten Bindemittel auf Silanbasis enthalten sind.1. Thixotropic, silane group-reactive, after cooling still viscous-plastic deformable hot melt adhesive, characterized in that it is a mixture of
- at least one thermoplastic material,
and
contains at least one thixotropic agent,
wherein silane groups are contained either in the thermoplastic material itself or in at least one additionally incorporated binder based on silane. 2. Schmelzklebstoff nach Anspruch 1, dadurch gekennzeichnet, dass das thermoplastische, Silangruppen enthaltende, makromolekulare Material ausgewählt ist aus der Gruppe, bestehend aus Polyamidharzen, Polyolefinen, Polyacrylaten, Polymethacrylaten und Polyurethanharzen, welche insbesondere aus folgenden Einzelkomponenten auf­gebaut sind: A) wenigstens einem isocyanatreaktiven Poly­urethanpräpolymeren, und B) wenigstens einer mit Isocyanatgruppen rea­gierenden, Silangruppen enthaltenden Verbindung, und/oder C) gegebenenfalls wenigstens einem Kettenver­längerer. 2. Hot melt adhesive according to claim 1, characterized in that the thermoplastic, silane group-containing, macromolecular material is selected from the group consisting of polyamide resins, polyolefins, polyacrylates, polymethacrylates and polyurethane resins, which are composed in particular of the following individual components: A) at least one isocyanate-reactive polyurethane prepolymer, and B) at least one compound which reacts with isocyanate groups and contains silane groups, and / or C) optionally at least one chain extender. 3. Schmelzklebstoff nach Anspruch 2, dadurch gekennzeichnet, dass die in Punkt A) erwähnten Polyurethan­präpolymeren aus folgenden Einzelkomponenten aufgebaut sind: a) aromatischen Diisocyanaten, wie z.B. 4,4′-­Diphenylmethandiisocyanat, 2,4-Toluoldiisocyanat, Naph­thylen-1,5-diisocyanat, 1,3- und 1,4-Phenylendiisocyanat, Triphenylmethan-4,4′,4˝-triisocyanat, Polyphenyl-poly­methylenpolyisocyanate, und/oder b) aliphatischen oder cycloaliphatischen Diiso­cyanaten, wie z.B. Hexamethylen-diisocyanat, 1,12-Dodecan­ diisocyanat, Cyclobutan-1,3-diisocyanat, Cyclohexan-1,3- und -1,4-diisocyanat, 1-Isocyanato-3,3,5-trimethyl-5-iso­cyanatomethylcyclohexan, 2,4- und 2,6-Hexahydrotoluylen­diisocyanat, Hexahydro-1,3- und -1,4-phenyldiisocyanat, Perhydro-2,4′- und -4,4′-diphenylmethandiisocyanat, und c) Polyolen mit einem Molekulargewichtsbereich von 400 bis 10'000, vorzugsweise von 1'000 bis 5'000, wie z.B. linearen oder verzweigten
- Polybutadienen,
- Polycarbonaten,
- Polycaprolactonen,
- Polycaprolactamen,
- Polyethern, beispielsweise Polyethylenoxide, Polypropylenoxide, Polybutylenoxide, Polystyroloxide, Polyepichlorhydrine, Polytetrahydrofurane,
- Polyestern, beispielsweise beliebige Konden­sationsprodukte von mehrwertigen Alkoholen - z.B. Ethylen­glycol, Propylenglykol-1,2 und -1,3, Butylenglykol-1,4 und -2,3, Hexandiol-1,6, Octandiol-1,8, Glycerin, Tri­methylolpropan, Pentaerythrit, Chinit, Mannit und Sorbit, Methylglycosid, Diethylenglykol, Polyethylenglykole, Di­propylenglykol, Polypropylenglykole - mit mehrwertigen Carbonsäuren und/oder Carbonsäureanhydriden und/oder Carbonsäureestern, - z.B. Bernsteinsäure, Adipinsäure, Korksäure, Azelainsäure, Sebacinsäure, Phthalsäure, Iso­phthalsäure, Trimellitsäure, Phthalsäureanhydrid, Tetra­hydrophthalsäureanhydrid, Tetrachlorphthalsäureanhydrid, Glutarsäureanhydrid, Maleinsäureanhydrid, Fumarsäure, Terephthalsäuredimethylester und Terephthalsäure-bis­glykolester -
mit jeweils wenigstens 2 endständigen primären und/oder sekundären OH-Gruppen, d) kurzkettigen Diolen mit endständigen primä­ren und/oder sekundären OH-Gruppen, wie z.B. Ethylen­glykol, bis-Hexandiol-1,6, Propylenglykol, bis-Hexapro­pylenglykol, Diethylenglykol, bis-Hexaethylenglykol, und/oder e) Vernetzern, wie z.B. Trimethylolpropan, Glyzerin, Hexantriol, Triethanolamin, Sorbit, Mannit, Sucrose, Ethylenamin, Ethanolamin, Hexamethylenamin, Pentaerythrit. 3. Hot melt adhesive according to claim 2, characterized in that the polyurethane prepolymers mentioned in point A) are composed of the following individual components: a) aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, naphthylene-1,5-diisocyanate, 1,3- and 1,4-phenylene diisocyanate, triphenylmethane-4,4 ', 4˝-triisocyanate , Polyphenyl-polymethylene polyisocyanates, and / or b) aliphatic or cycloaliphatic diisocyanates, such as hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3- and -1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, 2,4- and 2,6-hexahydrotoluenediisocyanate , Hexahydro-1,3- and -1,4-phenyl diisocyanate, perhydro-2,4'- and -4,4'-diphenylmethane diisocyanate, and c) polyols with a molecular weight range from 400 to 10,000, preferably from 1,000 to 5,000, such as linear or branched
- polybutadienes,
- polycarbonates,
- polycaprolactones,
- polycaprolactams,
Polyethers, for example polyethylene oxides, polypropylene oxides, polybutylene oxides, polystyrene oxides, polyepichlorohydrins, polytetrahydrofurans,
- Polyesters, for example any condensation products of polyhydric alcohols - for example ethylene glycol, 1,2 and -1,3 propylene glycol, 1,4 and 2,3 butylene glycol, 1,6-hexanediol, 1,8-octanediol, glycerol, trimethylolpropane , Pentaerythritol, quinite, mannitol and sorbitol, methyl glycoside, diethylene glycol, polyethylene glycols, dipropylene glycol, polypropylene glycols - with polyvalent carboxylic acids and / or carboxylic acid anhydrides and / or carboxylic acid esters, - for example succinic acid, adipic acid, suberic acid, azelaic acid, phthalic acid, sebacic acid acid, sebacic acid acid , Tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, glutaric anhydride, maleic anhydride, fumaric acid, dimethyl terephthalate and bisglycol terephthalate -
with at least 2 terminal primary and / or secondary OH groups, d) short-chain diols with terminal primary and / or secondary OH groups, such as, for example, ethylene glycol, 1,6-hexanediol, propylene glycol, bis-hexapropylene glycol, diethylene glycol, bis-hexaethylene glycol, and or e) crosslinking agents, such as trimethylolpropane, glycerol, hexanetriol, triethanolamine, sorbitol, mannitol, sucrose, ethylene amine, ethanolamine, hexamethylene amine, pentaerythritol. 4. Schmelzklebstoff nach einem der Ansprüche 2 bis 3, dadurch gekennzeichnet, dass die in Anspruch 2, Punkt B) erwähnten Verbindungen ausgewählt sind aus
difunktionellen Alkoxysilanen, wie z.B.
3-Aminopropylmethyl-dimethoxysilan,
3-Aminopropylmethyl-diethoxysilan,
N-Aminoethyl-3-aminopropyl-methyl-dimethoxy­silan,
3-Mercaptopropyl-methyl-dimethoxysilan,
3-Mercaptopropyl-methyl-diethoxysilan, usw.
und/oder aus
trifunktionellen Alkoxysilanen, wie z.B.
3-Aminopropyl-trimethoxysilan,
3-Aminopropyl-triethoxysilan,
3-Mercaptopropyl-trimethoxysilan,
3-Mercaptopropyl-triethoxysilan,
N-Methyl-3-aminopropyl-trimethoxysilan,
3-Amino-propylmethyl-diethoxysilan,
N-Aminoethyl-3-aminopropylmethyl-dimethoxysilan,
3-Glycidoloxypropyl-trimethoxysilan, usw.
und/oder aus
Silangruppen enthaltenden Verbindungen, die durch Umetherung der Silangruppen der oben erwähnten di- oder trifunktionellen Alkoxysilanen mit wenigstens einer H-aktiven Verbindunge gemäss Anspruch 3, Punkte c), d) oder e) erhältlich sind.4. Hot melt adhesive according to one of claims 2 to 3, characterized in that the compounds mentioned in claim 2, point B) are selected from
difunctional alkoxysilanes, such as
3-aminopropylmethyldimethoxysilane,
3-aminopropylmethyl-diethoxysilane,
N-aminoethyl-3-aminopropyl-methyl-dimethoxysilane,
3-mercaptopropyl-methyl-dimethoxysilane,
3-mercaptopropyl-methyl-diethoxysilane, etc.
and / or from
trifunctional alkoxysilanes, such as
3-aminopropyltrimethoxysilane,
3-aminopropyl-triethoxysilane,
3-mercaptopropyl-trimethoxysilane,
3-mercaptopropyl-triethoxysilane,
N-methyl-3-aminopropyltrimethoxysilane,
3-aminopropylmethyl diethoxysilane,
N-aminoethyl-3-aminopropylmethyldimethoxysilane,
3-glycidoloxypropyl trimethoxysilane, etc.
and / or from
Compounds containing silane groups, which are obtainable by transetherification of the silane groups of the above-mentioned di- or trifunctional alkoxysilanes with at least one H-active compound according to claim 3, points c), d) or e). 5. Schmelzklebstoff nach einem der Ansprüche 2 bis 4, dadurch gekennzeichnet, dass die in Anspruch 2, Punkt C) erwähnten Kettenverlängerer ausgewählt sind aus niedermolekularen, wenigstens di-H-aktiven Verbindungen, vorzugsweise effektiv di-H-aktive Verbindungen, wie z.B. Ethylenglykol, bis-Hexandiol-1,6, Propylenglykol, bis-He­xapropylenglykol, Diethylenglykol, bis-Hexaethylenglykol, N-Methylethanolamin, N-Ethylethanolamin, 2-Mercaptoetha­nol, Natriumchlorid-Komplex von p,p-Methylen-dianilin, der bei Temperaturen oberhalb von 80°C in die chemisch reaktive Form übergeführt wird - Caytur 21® - usw.5. Hot melt adhesive according to one of claims 2 to 4, characterized in that the chain extenders mentioned in claim 2, point C) are selected from low molecular weight, at least di-H-active compounds, preferably effectively di-H-active compounds, such as, for example Ethylene glycol, bis-hexanediol-1,6, propylene glycol, bis-hexapropylene glycol, diethylene glycol, bis-hexaethylene glycol, N-methylethanolamine, N-ethylethanolamine, 2-mercaptoethanol, sodium chloride complex of p, p-methylene dianiline, which is used at temperatures above from 80 ° C to the chemically reactive form - Caytur 21® - etc. 6. Schmelzklebstoff nach Anspruch 1, dadurch ge­kennzeichnet, dass das thermoplastische, keine Silangrup­pen enthaltende, makromolekulare Material ausgewählt ist aus der Gruppe, bestehend aus Polyamidharzen, Polyolefi­nen, Polyacrylaten, Polymethacrylaten und Polyurethanhar­zen, welche insbesondere aus folgenden Einzelkomponenten aufgebaut sind: a) aromatischen Diisocyanaten, wie z.B. 4,4′-­Diphenylmethandiisocyanat, 2,4-Toluoldiisocyanat, Naph­thylen-1,5-diisocyanat, 1,3- und 1,4-Phenylendiisocyanat, und/oder b) aliphatischen oder cycloaliphatischen Diiso­cyanaten, wie z.B. Hexamethylen-diisocyanat, 1,12-Dodecan­diisocyanat, Cyclobutan-1,3-diisocyanat, Cyclohexan-1,3- und -1,4-diisocyanat, 1-Isocyanato-3,3,5-trimethyl-5-iso­cyanatomethylcyclohexan, 2,4- und 2,6-Hexahydrotoluylen­diisocyanat, Hexahydro-1,3- und -1,4-phenyldiisocyanat, Perhydro-2,4′- und -4,4′-diphenylmethandiisocyanat, und c) Polyolen mit einem Molekulargewichtsbereich von 400 bis 10'000, vorzugsweise von 1'000 bis 5'000, wie z.B. linearen oder verzweigten
- Polybutadienen,
- Polycarbonaten,
- Polycaprolactonen
- Polycaprolactamen,
- Polyethern, beispielsweise Polyethylenoxide, Polypropylenoxide, Polybutylenoxide, Polystyroloxide, Polyepichlorhydrine, Polytetrahydrofurane,
- Polyestern, beispielsweise beliebige Konden­sationsprodukte von mehrwertigen Alkoholen - z.B. Ethylen­ glycol, Propylenglykol-1,2 und -1,3, Butylenglykol-1,4 und -2,3, Hexandiol-1,6, Octandiol-1,8, Glycerin, Tri­methylolpropan, Pentaerythrit, Chinit, Mannit und Sorbit, Methylglycosid, Diethylenglykol, Polyethylenglykole, Di­propylenglykol, Polypropylenglykole - mit mehrwertigen Carbonsäuren und/oder Carbonsäureanhydriden und/oder Carbonsäureestern, - z.B. Bernsteinsäure, Adipinsäure, Korksäure, Azelainsäure, Sebacinsäure, Phthalsäure, Iso­phthalsäure, Trimellitsäure, Phthalsäureanhydrid, Tetra­hydrophthalsäureanhydrid, Tetrachlorphthalsäureanhydrid, Glutarsäureanhydrid, Maleinsäureanhydrid, Fumarsäure, Terephthalsäuredimethylester und Terephthalsäure-bis-­glykolester -
mit jeweils endständigen primären und/oder se­kundären OH-Gruppen, wobei die OH-Funktionalität vorzugs­weise im Bereich um 2 liegt, und/oder d) kurzkettigen Diolen mit endständigen primä­ren und/oder sekundären OH-Gruppen, wie z.B. Ethylen­glykol, bis-Hexandiol-1,6, Propylenglykol, bis-Hexapro­pylenglykol, Diethylenglykol, bis-Hexaethylenglykol. 6. Hot melt adhesive according to claim 1, characterized in that the thermoplastic, macromolecular material containing no silane groups is selected from the group consisting of polyamide resins, polyolefins, polyacrylates, polymethacrylates and polyurethane resins, which are composed in particular of the following individual components: a) aromatic diisocyanates, such as 4,4'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, naphthylene-1,5-diisocyanate, 1,3- and 1,4-phenylene diisocyanate, and / or b) aliphatic or cycloaliphatic diisocyanates such as hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3- and -1,4-diisocyanate, 1-isocyanato-3,3,5 -trimethyl-5-isocyanatomethylcyclohexane, 2,4- and 2,6-hexahydrotoluenediisocyanate, hexahydro-1,3- and -1,4-phenyldiisocyanate, perhydro-2,4'- and -4,4'-diphenylmethane diisocyanate, and c) polyols with a molecular weight range from 400 to 10,000, preferably from 1,000 to 5,000, such as linear or branched
- polybutadienes,
- polycarbonates,
- polycaprolactones
- polycaprolactams,
Polyethers, for example polyethylene oxides, polypropylene oxides, polybutylene oxides, polystyrene oxides, polyepichlorohydrins, polytetrahydrofurans,
- Polyesters, for example any condensation products of polyhydric alcohols - for example ethylene glycol, propylene glycol 1,2 and 1,3, butylene glycol 1,4 and 2,3, hexanediol 1,6, octanediol 1,8, glycerin, trimethylolpropane, pentaerythritol, quinite, mannitol and sorbitol, methylglycoside, Diethylene glycol, polyethylene glycols, dipropylene glycol, polypropylene glycols - with polyvalent carboxylic acids and / or carboxylic acid anhydrides and / or carboxylic acid esters, - for example succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, titric acid, phthalic anhydride, phthalic anhydride Dimethyl terephthalate and bis-glycol terephthalate -
each with terminal primary and / or secondary OH groups, the OH functionality preferably being in the range around 2, and / or d) short-chain diols with terminal primary and / or secondary OH groups, such as, for example, ethylene glycol, 1,6-hexanediol, propylene glycol, bis-hexapropylene glycol, diethylene glycol, bis-hexaethylene glycol. 7. Schmelzklebstoff nach Ansprüchen 1 und 6, da­durch gekennzeichnet, dass das keine Isocyanatgruppen ent­haltende Bindemittel auf Silanbasis aus den in Anspruch 2, Punkte A) und B) erwähnten Materialien, vorzugsweise aus den in den Ansprüchen 3 und 4 erwähnten Materialien, auf­gebaut ist.7. Hot melt adhesive according to claims 1 and 6, characterized in that the silane-based binder containing no isocyanate groups is composed of the materials mentioned in claim 2, points A) and B), preferably of the materials mentioned in claims 3 and 4. 8. Schmelzklebstoff nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass das Thixotropiermittel aus der Gruppe bestehend aus Bentone, Russ, Kieselsäure­derivate, gefällte Kreiden, PVC, Harnstoffderivate, Acryl­derivate usw. ausgewählt sind.8. Hot melt adhesive according to one of claims 1 to 7, characterized in that the thixotropic agent is selected from the group consisting of bentones, carbon black, silica derivatives, precipitated chalks, PVC, urea derivatives, acrylic derivatives, etc. 9. Schmelzklebstoff nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass er zusätzlich noch
- wenigstens einen Weichmacher, vorzugsweise in einer Menge von 2 bis 30 Gew.-%, insbesondere in einer Men­ge von 5 bis 10 Gew.-%, und/oder
- wenigstens einen Füllstoff, vorzugsweise in einer Menge von 5 bis 50 Gew.-%, insbesondere in einer Menge von 8 bis 15 Gew.-%, und/oder
- wenigstens einen Zusatzstoff, vorzugsweise in einer Menge von 0,001 bis 5 Gew.-%,
enthält, wobei sich die genannten Prozentanga­ben auf den gesamten Schmelzklebstoff beziehen.9. hot melt adhesive according to one of claims 1 to 8, characterized in that it additionally
at least one plasticizer, preferably in an amount of 2 to 30% by weight, in particular in an amount of 5 to 10% by weight, and / or
at least one filler, preferably in an amount of 5 to 50% by weight, in particular in an amount of 8 to 15% by weight, and / or
at least one additive, preferably in an amount of 0.001 to 5% by weight,
contains, the percentages given refer to the entire hot melt adhesive. 10. Schmelzklebstoff nach Anspruch 9, dadurch gekennzeichnet, dass
- der Weichmacher ausgewählt ist aus der Gruppe, bestehend aus Phthalaten, wie etwa Dibutyl-, Dioctyl-, Dicyclohexyl-, Diisooctyl-, Diisodecyl-, Dibenzyl- oder Butylbenzylphthalat, Phosphaten mit bis zu 8 C-Atomen im Alkylrest, wie Trioctylphosphat; epoxyhaltige Weichmacher, Toluolsulfonamiden, Chlorparaffinen, Adipinsäureestern, Rizinusölen usw.;
- der Füllstoff ausgewählt ist aus der Gruppe mit Kieselsäurederivate, Gips, Talkum, Aktivkohle, Metall­pulver, Kreide, Keoline, Russe, usw.;
- der Hilfs- bzw. Zusatzstoff ausgewählt ist aus a) Haftvermittlern, insbesondere Silan-haltige Verbindungen, welche zusätzlich noch wenigstens eine reaktive Gruppe, wie Epoxy-, Isocyanat-, Amin-, Doppel­bindungsgruppen usw., enthalten können, b) Farbstoffen oder Pigmenten, c) üblichen Polyurethankatalysatoren, wie Blei- und/oder Zinnverbindungen, gegebenenfalls unter Mitver­wendung weiterer Polyurethankatalysatoren, insbesondere von tert. Amin-haltigen Katalysatoren, d) UV-Absorptionsmitteln oder Stabilisatoren, wie phenolische Antioxidantien, Lichtschutzmitteln, e) oberflächenaktiven Zusatzstoffen, wie Emul­gatoren, f) Flammschutzmitteln, und g) fungistatisch und/oder bakteriostatisch wirkenden Substanzen. 10. Hot melt adhesive according to claim 9, characterized in that
- The plasticizer is selected from the group consisting of phthalates, such as dibutyl, dioctyl, dicyclohexyl, diisooctyl, diisodecyl, dibenzyl or butylbenzyl phthalate, phosphates with up to 8 carbon atoms in the alkyl radical, such as trioctyl phosphate; plasticizers containing epoxy, toluenesulfonamides, chlorinated paraffins, adipic acid esters, castor oils, etc .;
- The filler is selected from the group consisting of silicic acid derivatives, gypsum, talc, activated carbon, metal powder, chalk, Keoline, Russian, etc .;
- The auxiliary or additive is selected from a) adhesion promoters, in particular silane-containing compounds, which may additionally contain at least one reactive group, such as epoxy, isocyanate, amine, double bond groups, etc., b) dyes or pigments, c) customary polyurethane catalysts, such as lead and / or tin compounds, optionally with the use of further polyurethane catalysts, in particular tert. Amine-containing catalysts, d) UV absorbers or stabilizers, such as phenolic antioxidants, light stabilizers, e) surface-active additives, such as emulsifiers, f) flame retardants, and g) fungistatic and / or bacteriostatic acting substances. 11. Verfahren zur Herstellung eines thixotro­pierten, Silangruppen-reaktiven Schmelzklebstoffes nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass man unter wasserfreien Bedingungen entweder a) ein thermoplastisches, Silangruppen enthal­tendes Material vorlegt oder es in situ vor oder nach der Hinzugabe von weiteren Komponenten erzeugt, und danach beim Erwei­chungspunkt das Thixotropiermittel homogen einmischt, oder b) wenigstens ein Isocyanatgruppen und Silan­gruppen enthaltendes Material mit wenigstens einem Thixo­tropiermittel vermischt, danach wenigstens eine minde­stens di-H-aktive Verbindung hinzugibt und die Isocyanat­gruppen in situ umsetzt, oder c) ein thermoplastisches, keine Silangruppen ent­haltendes Material vorlegt oder es in situ erzeugt, da­nach beim Erweichungspunkt das keine Isocyanatgruppen ent­haltende Bindemittel auf Silanbasis und das Thixotropier­mittel homogen einmischt, und
die gemäss obigen Varianten a) bis c) hergestell­ten Gemische auf Umgebungstemperatur erkalten lässt. 11. A method for producing a thixotropic, silane group-reactive hot melt adhesive according to any one of claims 1 to 10, characterized in that either under anhydrous conditions a) presenting a thermoplastic material containing silane groups or producing it in situ before or after the addition of further components, and then homogeneously mixing in the thixotropic agent at the softening point, or b) at least one material containing isocyanate groups and silane groups is mixed with at least one thixotropic agent, then at least one at least di-H-active compound is added and the isocyanate groups are reacted in situ, or c) presenting a thermoplastic material containing no silane groups or producing it in situ, then homogeneously mixing in the silane-based binder containing no isocyanate groups and the thixotropic agent at the softening point, and
the mixtures prepared according to variants a) to c) above can cool to ambient temperature. 12. Verwendung des thixotropierten, Silangrup­pen-reaktiven Schmelzklebstoffes nach einem der Ansprüche 1 bis 10, zum Verkleben und/oder Abdichten von einem oder mehreren Materialien gleicher oder ungleicher Beschaffen­heit zu einem Verbund.12. Use of the thixotropic, silane group-reactive hot melt adhesive according to one of claims 1 to 10, for bonding and / or sealing one or more materials of the same or different properties to form a composite. 13. Verwendung nach Anspruch 12, dadurch gekenn­zeichnet, dass die zu verklebenden und/oder abzudichten­den Materialien ausgewählt sind aus der Gruppe, bestehend aus
- irgendeinem Glas, insbesondere Fahrzeugschei­ben, Verbundglasscheiben, Fassadenverglasungen,
- irgendeinem Metall, welches lackiert, metalli­siert oder sonstwie beschichtet und/oder vorbehandelt sein kann, z.B. Fahrzeugkarrosserien,
- irgendeiner Metall-Legierung, welche lackiert, metallisiert oder sonstwie beschichtet und/oder vorbehan­delt sein kann, z.B. Fahrzeugkarrosserien,
- irgendeinem Kunststoff,
- irgendeinem Baumaterial, insbesondere Steine, Beton, Mörtel, Strassenbeläge, und
- irgendeinem Holz.13. Use according to claim 12, characterized in that the materials to be glued and / or sealed are selected from the group consisting of
- any glass, in particular vehicle panes, laminated glass panes, facade glazing,
- any metal that can be painted, metallized or otherwise coated and / or pretreated, eg vehicle bodies,
any metal alloy which can be painted, metallized or otherwise coated and / or pretreated, for example vehicle bodies,
- some plastic,
- any building material, in particular stones, concrete, mortar, road surfaces, and
- some wood. 14. Verwendung nach Anspruch 12, dadurch ge­kennzeichnet, dass der Schmelzklebstoff am Applikations­ort mittels einer Verarbeitungsvorrichtung, beispiels­weise mittels einer Kartusche, welche beheizbar ist oder vorgewärmt worden ist, oder mittels einer Schmelzkleb­stoff-Applikationsanlage, bei einer für die Aufbringungen geeigneten, in der Nähe des Erweichungspunktes liegenden Temperatur auf die zu verklebenden und/oder abzudichten­den Materialien aufgebracht wird.14. Use according to claim 12, characterized in that the hot melt adhesive at the application site by means of a processing device, for example by means of a cartridge which can be heated or has been preheated, or by means of a hot melt adhesive application system, in a suitable for the applications, near the Softening point lying temperature is applied to the materials to be bonded and / or sealed. 15. Verwendung nach Anspruch 12, dadurch ge­kennzeichnet, dass der Schmelzklebstoff in Form eines Klebeprofils bei Umgebungstemperatur auf die zu verkle­benden und/oder abzudichtenden Materialien aufgebracht wird.15. Use according to claim 12, characterized in that the hot melt adhesive is applied in the form of an adhesive profile at ambient temperature to the materials to be bonded and / or sealed. 16. Verwendung nach Anspruch 15, dadurch ge­kennzeichnet, dass das Klebeprofil die Form einer Schnur oder eines Bandes hat, wobei zur Gewährleistung der Di­mensionsstabilitäten ein Faden oder ein Gitter irgend­welcher Beschaffenheit in die Schnur oder das Band ein­verleibt sein kann.16. Use according to claim 15, characterized in that the adhesive profile has the shape of a cord or a band, wherein a thread or a lattice of any kind can be incorporated into the cord or the band to ensure the dimensional stability.
EP87116213A 1987-10-09 1987-11-04 Reactive thixotropic hot-melt adhesive based on silane Expired - Lifetime EP0310704B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH396487 1987-10-09
CH3964/87 1987-10-09

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EP0310704A2 true EP0310704A2 (en) 1989-04-12
EP0310704A3 EP0310704A3 (en) 1989-12-06
EP0310704B1 EP0310704B1 (en) 1994-06-01

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EP (1) EP0310704B1 (en)
JP (1) JPH01115977A (en)
AT (1) ATE106418T1 (en)
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BR (1) BR8705968A (en)
CA (1) CA1312408C (en)
DE (1) DE3789964D1 (en)
ES (1) ES2053503T3 (en)
MX (1) MX168283B (en)
PT (1) PT86089B (en)
ZA (1) ZA878302B (en)

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US9212300B2 (en) 2007-08-10 2015-12-15 Henkel Ag & Co. Kgaa Reactive hot melt adhesive
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EP0450105A1 (en) * 1990-03-29 1991-10-09 Adco Products, Inc. Room-temperature, moisture-curable, primerless, poluyrethane-based adhesive composition and method
EP0533275A2 (en) * 1991-09-17 1993-03-24 ENICHEM SYNTHESIS S.p.A. Diol-terminated polycarbonates and their use in reactive adhesive and/or sealing formulations
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US5747581A (en) * 1992-03-28 1998-05-05 Proebster; Manfred Adhesive and sealing material
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WO1994007933A1 (en) * 1992-10-02 1994-04-14 Essex Specialty Products, Inc. Primer composition for improving the bonding of urethane adhesives to acid resistant paints
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US9365751B2 (en) 2012-07-24 2016-06-14 Henkel IP & Holding GmbH Reactive hot melt adhesive
US9428677B2 (en) 2013-01-24 2016-08-30 Henkel IP & Holding GmbH Reactive hot melt adhesive

Also Published As

Publication number Publication date
US4871590A (en) 1989-10-03
AU601509B2 (en) 1990-09-13
JPH01115977A (en) 1989-05-09
PT86089B (en) 1993-05-31
ES2053503T3 (en) 1994-08-01
AU8086287A (en) 1989-04-13
CA1312408C (en) 1993-01-05
DE3789964D1 (en) 1994-07-07
EP0310704A3 (en) 1989-12-06
PT86089A (en) 1989-07-31
ATE106418T1 (en) 1994-06-15
MX168283B (en) 1993-05-14
EP0310704B1 (en) 1994-06-01
ZA878302B (en) 1988-07-27
BR8705968A (en) 1989-05-30

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